Method of synthesizing zirconium-loaded fibrous adsorbent materials having phosphoryl groups and removal of objectionable substances using the adsorbents

ABSTRACT

A zirconium-loaded fibrous adsorbent material having phosphoryl groups which is produced by first grafting a reactive monomer having phosphoryl groups onto a polymeric substrate and then loading zirconium. One or more methods of using the zirconium-loaded fibrous adsorbent material to recover arsenic, phosphoric ions, and/or fluoride ions are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No. 10/732,232filed in the U.S. Patent and Trademark Office on Dec. 11, 2003 now U.S.Pat. No. 7,335,623, which claims the priority benefit of Japanese PatentApplication No. 2002-358915 filed on Dec. 11, 2002 in Japan. The entirecontents of each of these applications (U.S. Ser. No. 10/732,232 andJapanese Patent Application No. 2002-358915) are incorporated herein byreference in their entirety.

BACKGROUND

This invention relates to an adsorbent material for recovering andremoving objectionable substances, in particular, arsenic that arecontained in environmental water and liquid wastes such as waste waterfrom plants. One or more embodiments of the invention also relate to amethod of synthesizing the adsorbent material.

Research and development efforts have recently been made on materialscapable of trapping metals contained in environmental water bodies suchas rivers and the sea and this has led to the discovery that cationexchange resins using phosphoric acid as exchange groups can adsorbmetal ions present in rivers, lakes and wastewater from plants (see, forexample, Akinori Joh et al., “Cation exchange resins using phosphoricacid as exchange groups—Their selectivity for metal ions andapplications” in PHOSPHORUS LETTER, Japanese Association of InorganicPhosphorus Chemistry, Feb. 1, 2001, vol. 40, pp. 16-21).

Further, the present inventors developed a metal adsorbent material thathad a monomer with phosphoryl groups grafted onto a polymeric substrate(see, for example, Japanese Patent Application No. 2002-262502).

In the art of recovering and removing objectionable substances in theenvironment, particularly arsenic, two major methods have so far beenpracticed, one relying upon coagulating sedimentation and the otherusing chelating resins (see, for example, Xiaoping Zhu et al., “Removalof arsenic(V) by zirconium(IV)-loaded phosphoric acid chelating resin”in “SEPARATION SCIENCE AND TECHNOLOGY”, America, Marcel Dekker, Inc.,2001, 36(14), pp. 3175-3189).

However, the conventional adsorbent materials can adsorb arsenic onlyslowly. If arsenic is recovered and removed by coagulating sedimentationor with the aid of adsorbent materials in bead form, considerableinconvenience in handling has been met during the process of removal orin subsequent operations.

In addition, the conventional arsenic adsorbent materials are mostlysynthesized by common radical polymerization and their structure foradsorption of arsenic is so unstable that it is prone to leak out evenif it is adsorbed.

According to the Basic Environment Law which provides for the waterquality guidelines for public waters, arsenic should not be dischargedat concentrations higher than 0.1 ppm and its content in the environmentshould not exceed 0.01 ppm. Thus, the removal of arsenic is absolutelynecessary.

SUMMARY OF EMBODIMENTS OF THE INVENTION

An object, therefore, of one or more embodiments of the presentinvention is to provide an adsorbent material that allows for fasteradsorption of arsenic and anion such as phosphoric ion and which canremove them even if they are present at extremely low concentrations.

Another object of one or more embodiments of the invention is to providean adsorbent material that is easy to handle during or after adsorptiveremoval of arsenic and which is capable of efficient adsorption ofarsenic.

In order to attain those objects, the present inventors made intensivestudies and completed the present invention which relates to azirconium-loaded fibrous adsorbent material having phosphoryl groups.

The zirconium-loaded fibrous adsorbent material of one or moreembodiments of the invention having phosphoryl groups is produced byfirst grafting a reactive monomer having phosphoryl groups onto apolymeric substrate and then loading zirconium.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawing figures are non-limiting and illustrative of one or moreembodiments of the claimed invention.

FIG. 1 is a graph showing the pH dependency of the performance of thezirconium-loaded adsorbent material of an embodiment of the invention inadsorbing arsenic;

FIG. 2 is a graph showing the dependency on flow rate of arsenicadsorption by the zirconium-loaded adsorbent material an embodiment ofthe invention; and

FIG. 3 is a graph showing the dependency on arsenic's concentration ofthe zirconium-loaded adsorbent material of an embodiment of theinvention.

FIG. 4 is a graph showing the phosphoric ion adsorption characteristicsof the adsorbent material of an embodiment of the invention.

FIG. 5 is a breakthrough curve of phosphoric ion on the adsorbentmaterial of an embodiment of the invention.

FIG. 6 is a breakthrough curve of fluoride ion on the adsorbent materialof an embodiment of the invention.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The adsorbent material of one or more embodiments of the invention is azirconium-loaded fibrous adsorbent material having phosphoryl groups andit is produced by first grafting a reactive monomer having phosphorylgroups onto a polymeric substrate and then loading zirconium.

In one or more embodiments of the invention, fibers of polypropylene,polyethylene, polyester or composites thereof can be used as thepolymeric substrate and they may take on various forms including shortfiber, filament, nonwoven fabric or woven fabric.

The first step in the synthesis of the adsorbent material of one or moreembodiments of the invention is preparing an adsorbent precursor(hereunder sometimes referred to as the “graft product”) by grafting areactive monomer having phosphoryl groups onto the polymeric substrate.

1. Preparing the Adsorbent Precursor (Graft Product)

The method for preparing the graft product may comply with theconditions for synthesis disclosed in Japanese Patent Application No.2002-262502. Specific procedures and conditions of the method aredescribed below.

A monomer having mono- or difunctional phosphoryl groups may beintroduced into the polymeric substrate and specific examples include:

mono(2-methacryloyloxyethyl)acid phosphateCH₂═C(CH₃)COO(CH₂)₂OPO(OH)₂;di(2-methacryloyloxyethyl)acid phosphate[CH₂═C(CH₃)COO(CH₂)₂O]₂PO(OH);mono(2-acryloyloxyethyl)acid phosphateCH₂═CHCOO(CH₂)₂OPO(OH)₂;di(2-acryloyloxyethyl)acid phosphate[CH₂═CHCOO(CH₂)₂O]₂PO(OH); andmixed monomers thereof.

In the case of using mixed monomers, the mixing ratios of the respectivemonomers may be changed appropriately.

A type of monomer having the following structure may also be used as thereactive monomer:CH₂═C(CH₃)COO(CH₂)_(l)OCO—R—CO—OPO(OH)R′,wherein R is an optionally substituted (CH₂)_(m) or C₆H₄; R′ is ahydroxyl group or CH₂═C(CH₃)COO(CH₂)_(n)OCO—R—CO—O— group; l, m and nare each independently an integer of 1-6.

Graft polymerization can be effected by first generating reaction activepoints in the polymeric substrate and then bringing it into contact withthe reactive monomer.

Reaction active points can be generated by either one of the followingmethods (a)-(c).

(a) Exposure to Radiation

The polymeric substrate as preliminarily nitrogen purged is exposed toradiation in a nitrogen atmosphere either at room temperature or undercooling with Dry Ice. The radiation to be employed is electron beams orγ-rays. The exposure dose may be determined appropriately on thecondition that it be sufficient to generate reaction active points andit is typically in the range of 50-200 kGy.

(b) Exposure to Plasma

The polymeric substrate as preliminarily nitrogen purged is exposed toplasma in a nitrogen atmosphere at room temperature. The exposurecontinues for 1-24 hours using rf waves at 10 MHz or higher.

(c) Use of Initiator

Under nitrogen bubbling, reaction active points are generated using aradical initiator at between room temperature and 50° C. Exemplaryradical initiators include azobisisobutyronitrile and benzoyl peroxide.

While graft polymerization can be effected in a nitrogen atmosphere, theconcentration of oxygen in the atmosphere is preferably low in order toachieve higher values of percent grafting. The term “percent grafting”as used herein means the ratio in weight percentage of the reactivemonomer to the polymeric substrate onto which it has been grafted. Thereaction temperature which depends on the reactivity of the reactivemonomer is generally between 40 and 60° C. The concentration of themonomer suffices to range from 10 to 30% of the solvent. The reactiontime which is generally 1-48 hours can be determined depending upon thereaction temperature and the percent grafting required.

2. Synthesis of the Zirconium-Loaded Adsorbent Material

The adsorbent material of one or more embodiments of the invention canbe produced by loading the thus prepared graft product with zirconium.

The graft product is subjected to passage of a zirconium compound insolution at a pH of 0.5-2 for 1-24 hours at a flow rate of 100 mL/h. Thezirconium compound that can be used in one or more embodiments of theinvention is a zirconium(IV) compound, a zirconium(III) compound or azirconium(II) compound and may be exemplified by zirconic acid,zirconate (a conventoinal oxo-acid salt of zirconium(IV)), zirconate(which is not an oxo-acid of zirconium), etc. Specific examples ofzirconium compounds in solution include solutions of zirconium nitrate,zirconium sulfate, zirconium chloride and zirconium oxide, as well as ananalytical standard solution of zirconium. The concentration ofzirconium compounds in solution can be adjusted appropriately.

In order to subject the graft product to passage of zirconium compoundsin solution, any means known to the skilled artisan may be employed,such as stirring the solution in which the graft product is immersed orpassing the solution through a column packed with the graft product.Preferably, the desired product can be obtained by stirring 10 mmol/L ofzirconium nitrate in solution at a pH of 1 for one hour as it containsthe graft product immersed therein or by passing the solution through acolumn packed with the graft product.

The arsenic adsorption characteristics of the adsorbent material of oneor more embodiments of the invention are depicted in FIGS. 1-3.

FIG. 1 is a graph showing the pH dependency of arsenic adsorption atvarying pHs of an arsenic containing liquor. As one can see from FIG. 1,the adsorbent material of one or more embodiments of the invention canadsorb arsenic at pHs of 1-9 and its adsorbing capability is by no meansdependent on pH. It can also be seen that the difference in absorbingcapability is particularly small in the acidic range below pH=7. At eachof the tested pH values, the absorbing capability of the adsorbentmaterial saturated and substantially leveled off when the amount of theeffluent was about 130 times the volume of the sample.

FIG. 2 is a graph showing the dependency on flow rate of arsenicadsorption at varying flow rates of an arsenic containing liquor. As onecan see from FIG. 2, the adsorbing capability was maintained when thearsenic containing liquor was passed at space velocities of 64-1300 1/hand this indicates that arsenic could be adsorbed without leakage evenat high treatment speeds. The data in FIG. 2 shows the feasibility ofthe adsorbent material of one or more embodiments of the invention inlarge-scale, high-speed treatments as in plants.

FIG. 3 is a graph showing the concentration dependency of arsenicadsorption at varying concentrations of arsenic in an arsenic containingliquor. As one can see from FIG. 3, the adsorbing capability of theadsorbent material of an embodiment of the invention does not vary muchat arsenic concentrations of 1-5 mmol/L and can be maintainedindependent of the concentration of the treating liquor.

Thus, FIGS. 1-3 show that the adsorbent material of one or moreembodiments of the invention exhibits high adsorbing capabilityindependent of the concentration of the treating liquor, the pH and thetreating speed.

The following examples are provided for further illustrating one or moreembodiments of the present invention but are in no way to be taken aslimiting.

Example 1

A nonwoven fabric as a polymeric substrate was subjected to graftpolymerization and the resulting graft product in nonwoven fabric formwas rendered wet by passing pure water. In the process of preparing thegraft product, the conversion (the degree of grafting) was 100-400% andphosphoryl groups were introduced in amounts of 4-8 mmol/g.Subsequently, the graft product was packed into an adsorption column,through which an aqueous solution of zirconium nitrate (10 mmol/L, pH=2)was passed for one hour at a flow rate of 100 mL/h so as to load thegraft product with zirconium. Thereafter, the column was washed withpure water until the pH of the effluent was between 5 and 7, therebyyielding a zirconium-loaded adsorbent material. The zirconium loadingwas 4.2 mmol/g. The adsorbent material produced in Example 1 using thenonwoven fabric is not only usable as a filter on its own; the scope ofits applications can be widened by processing it into various shapes ormaking a laminate of it.

Example 2

Polyethylene short fiber was used as a polymeric substrate, onto which areactive monomer having phosphoryl groups was grafted to prepare a graftproduct. The degree of grafting was 100-300% and phosphoryl groups wereintroduced in amounts of 1-8 mmol/g. An aqueous solution of zirconiumpreliminarily adjusted to 10 mmol/L was treated with nitric acid to havea pH of 1. The fibrous graft product was immersed in that acidic aqueoussolution of zirconium, which was then stirred for 1-24 hours at 25° C.The zirconium-loaded adsorbent material was obtained and it was found tohave zirconium introduced in an amount of 4.0 mmol/g.

The adsorbent material produced in Example 2 using the short fiber hasgood processability and can be packed into various types of modulesincluding columns, thus expanding the scope of its applications.

The adsorbent material of one or more embodiments of the presentinvention is synthesized by utilizing graft polymerization, so acrosslinked structure can be easily formed within the adsorbentmaterial. Since this facilitates immobilization of zirconium which isresponsible for adsorbing arsenic, not only the arsenic contained in theenvironment such as natural water but also other objectionablesubstances including antimony and negatively charged ions such asfluoride and chloride ions can be easily removed, thus adding potentialuses including prevention of environmental pollution and purification ofpotable water.

Unlike the conventional adsorbent materials that must be processed intomodules for practical use, the adsorbent material of one or moreembodiments of the invention can be directly used as a filter andpermits easy handling.

Example 3

The phosphoric ion adsorption characteristics of the adsorbent materialof one or more embodiments of the invention are depicted in FIG. 4. Itwas depicted by subjecting the material to a passage of phosphoric ioncontaining liquors at a pH of 1.5 having various phosphoric ionconcentrations at varying contact time. Compared with the prior methodof adsorbing phosphoric ions by using a zirconium-loaded activatedcarbon, the rate of adsorption obtained by the adsorbent material of oneor more embodiments of the invention is so high that the percentage ofadsorption attained up to about 100% in 2 hours.

The breakthrough curve of phosphoric ion on the adsorbent material ofone or more embodiments of the invention was depicted in FIG. 5. Asshown in FIG. 5, when the adsorbent material of one or more embodimentsof the invention was packed into a column, through which a phosphoricion containing liquor was passed, no phosphoric ion was leakedindependent of the phosphoric ion concentration in the liquor.

Example 4

Adsorption experiment was conducted on the adsorbent material of one ormore embodiments of the invention by using a fluoride ion containingliquor. The liquor was prepared by adjusting pH of a standard solutionof fluorine (10 mmol) to 7. The breakthrough curve of fluoride ion onthe adsorbent material was depicted in FIG. 6. The adsorbent material ofone or more embodiments of the invention was packed into a column,through which the liquor was passed at flow rate of 1300 h⁻¹, 240 h⁻¹,and 64 h⁻¹, in result, the breakthrough point was about 50 independentof the flow rate of the liquor.

1. A method of recovering arsenic using a zirconium-loaded fibrousadsorbent material having phosphoryl groups, which comprises subjectingsaid adsorbent material to passage of an arsenic containing liquor at aspace velocity of 64-1300 [1/h] under acidic conditions at a pH of lessthan
 7. 2. A method of recovering phosphoric ion using azirconium-loaded fibrous adsorbent material having phosphoryl groups,which comprises subjecting said adsorbent material to passage of aphosphoric ion containing liquor at a space velocity of 64-1300 [1/h]under acidic conditions at a pH of about 1.5.
 3. A method of recoveringfluoride ion using a zirconium-loaded fibrous adsorbent material havingphosphoryl groups, which comprises subjecting said adsorbent material topassage of a fluoride ion containing liquor at a space velocity of64-1300 [1/h] under acidic conditions at a pH of less than
 7. 4. Themethod of claim 1, wherein the zirconium-loaded fibrous adsorbentmaterial has a zirconium content in an amount of 4.0 or 4.2 mmol/g. 5.The method of claim 4, wherein the fibrous material is selected from thegroup consisting of a fiber, a filament, a nonwoven fabric and a wovenfabric.
 6. The method of claim 5, wherein the fiber is selected from thegroup consisting of polypropylene, polyethylene and polyester.
 7. Themethod of claim 5, wherein the fiber is selected from the groupconsisting of polypropylene and polyethylene.
 8. The method of claim 1,wherein the phosphoryl group is selected from the group consisting ofmono(2-methacryloyloxyethyl)acid phosphate,di(2-methacryloyloxyethyl)acid phosphate, mono(2-acryloyloxyethyl)acidphosphate, di(2-acryloyloxyethyl)acid phosphate, and mixtures thereof.9. The method of claim 1, wherein the phosphoryl groups of thezirconium-loaded fibrous adsorbent material are phosphoryl groups of areactive monomer comprising a material of formula:CH₂=C(CH₃)COO(CH₂)_(l)OCO—R—CO—OPO(OH)R′ wherein R is an optionallysubstituted (CH₂)_(m) group or C₆H₄ group, wherein R′ is a hydroxylgroup or a CH₂═C(CH₃)COO(CH₂)_(n)OCO—R—CO—O— group, wherein l, m and nare each independently an integer of 1-6.
 10. The method of claim 1,wherein the wherein the fibrous material is a filter.
 11. The method ofclaim 2, wherein the zirconium-loaded fibrous adsorbent material has azirconium content in an amount of 4.0 or 4.2 mmol/g.
 12. The method ofclaim 2, wherein the fibrous material is selected from the groupconsisting of a fiber, a filament, a nonwoven fabric and a woven fabric.13. The method of claim 12, wherein the fiber is selected from the groupconsisting of polypropylene, polyethylene and polyester.
 14. The methodof claim 2, wherein the phosphoryl group is selected from the groupconsisting of mono(2-methacryloyloxyethyl)acid phosphate,di(2-methacryloyloxyethyl)acid phosphate, mono(2-acryloyloxyethyl)acidphosphate, di(2-acryloyloxyethyl)acid phosphate, and mixtures thereof.15. The method of claim 2, wherein the phosphoryl groups of thezirconium-loaded fibrous adsorbent material are phosphoryl groups of areactive monomer comprising a material of formula:CH₂═C(CH₃)COO(CH₂)_(l)OCO—R—CO—OPO(OH)R′ wherein R is an optionallysubstituted (CH₂)_(m) group or C₆H₄ group, wherein R′ is a hydroxylgroup or a CH₂═C(CH₃)COO(CH₂)_(n)OCO—R—CO—O— group, wherein l, m and nare each independently an integer of 1-6.
 16. The method of claim 2,wherein fibrous material is a filter.